WO2020127079A1 - Procédé de polymérisation haute pression de monomères à insaturation éthylique dans un réacteur de polymérisation - Google Patents

Procédé de polymérisation haute pression de monomères à insaturation éthylique dans un réacteur de polymérisation Download PDF

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Publication number
WO2020127079A1
WO2020127079A1 PCT/EP2019/085394 EP2019085394W WO2020127079A1 WO 2020127079 A1 WO2020127079 A1 WO 2020127079A1 EP 2019085394 W EP2019085394 W EP 2019085394W WO 2020127079 A1 WO2020127079 A1 WO 2020127079A1
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Prior art keywords
reactor
blow down
vessel
fluid communication
polymerization
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PCT/EP2019/085394
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English (en)
Inventor
Dieter Littmann
Andre-Armand Finette
Christoph Wolf
Michael Deuerling
Juergen MOHRBUTTER
Danir KHAYRULLIN
Giulia Mei
Erich Neumann
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Basell Polyolefine Gmbh
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Application filed by Basell Polyolefine Gmbh filed Critical Basell Polyolefine Gmbh
Priority to CN201980078729.1A priority Critical patent/CN113166283B/zh
Priority to EP19818105.9A priority patent/EP3898708B1/fr
Priority to US17/312,288 priority patent/US20220106418A1/en
Publication of WO2020127079A1 publication Critical patent/WO2020127079A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/002—Component parts of these vessels not mentioned in B01J3/004, B01J3/006, B01J3/02 - B01J3/08; Measures taken in conjunction with the process to be carried out, e.g. safety measures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/03—Pressure vessels, or vacuum vessels, having closure members or seals specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/0027—Pressure relief
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/04—High pressure, i.e. P > 50 MPa, 500 bars or 7250 psi

Definitions

  • the present disclosure relates to a process for polymerizing or copolymerizing ethyleni- cally unsaturated monomers to obtain an ethylene-based polymer in a high-pressure polymeriza tion system comprising a continuously operated polymerization reactor.
  • Polyethylene is the most widely used commercial polymer. It can be prepared by a couple of different processes. Polymerization in the presence of free-radical initiators at elevated pressures was the method first discovered to obtain polyethylene and continues to be a valued process with high commercial relevance for the preparation of low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • a common set-up of a plant for preparing low density polyethylene comprises, besides a polymerization reactor which can be an autoclave or a tubular reactor or a combination of such reactors, further equipment.
  • a polymerization reactor which can be an autoclave or a tubular reactor or a combination of such reactors, further equipment.
  • a primary compressor and a secondary compressor which is sometimes designated as hyper compressor, is used.
  • a high-pressure polymeri zation unit normally further includes apparatuses like extruders and granulators for pelletizing the obtained polymer.
  • such a polymerization unit generally also comprises means for feeding monomers and comonomers, free-radical initiators, modifiers or other substances at one or more positions to the polymerization reaction.
  • Plants for preparing polyethylene are regularly constructed in a manner to be run continuously for long periods of time without any signs of fa tigue, thus, in general allowing rather long maintenance intervals.
  • the polymerization process in a LDPE reactor is carried out at high pressures which can reach 350 MPa.
  • high pressure requires special technology for the process to be han dled in a safe and reliable manner.
  • ethylene can decompose rapidly in an explosive manner to give soot, methane and hydro gen.
  • the drastic increase in pressure and temperature associated therewith - decomposition tem peratures can be excessively high (>1000°C) - represents a considerable potential risk for the operational safety of the production plants.
  • the temperatures reached during such a decomposition event can damage the reactor tubes, e.g. it may cause the tube metal to aus- tenize.
  • martensite At temperatures at which the metal austenizes, martensite is being formed in the reactor tubes, if the material is cooled rapidly. Martensite is the hardest and most brittle of the various mi crostructures found in carbon steels. Therefore, rapid removal of the hot gas produced by decomposition is believed to be essential during emergency blowdown.
  • a unidirectional blow down system comprising a front emergency blowdown valve located downstream from a hyper compressor discharge and in the front end of the reactor, and at least one additional valve at the end of the reactor.
  • the system shall prevent the reactor walls from reaching a temperature capable of causing the tube metal to austenize by maintaining flow in a single direction away from the hyper compressor during the blowdown process, and by maintaining specific pressure and flow velocity within the reactor during blowdown. In this manner the amount of heat transfer to the tube reactor shall be minimized.
  • the polymerization process is usually interrupted and the polymerization plant is depressurized.
  • the detection of leakages can, for example, be accomplished by IR point detectors as disclosed in WO 2017/194491 A1 .
  • depressurization sys tems make use of a so-called blow down vessel, which is located inside a so-called reactor bay. Regularly, in case of an emergency, the shutdown requires to depressurize both the secondary compressor and the reactor.
  • EP 0 272 512 A2 discloses that it is also possible to divide the high pressure polymerization system into a plurality of isolated sections at the same time as shutdown is triggered and only the section in which the shutdown is triggered is depressurized.
  • the reactor content comprising both hot ethylene and hot polymer is disposed into the reactor blow down ves sel via one or more emergency expansion valves in order to quench the hot gases with water and to separate the waste polymer from ethylene.
  • EP 0 266 543 A2 discloses that the depressurized reaction mixture is passed through at least two separating tanks installed in se ries, before reaching the atmosphere.
  • the blow down vessel In order to empty the blow down vessel from the polymer water slurry retained therein, it is common practice to open the blow down vessel which in turn re quires to fully depressurize the reactor and all other systems connected to the reactor and to purge free of hydrocarbons the reactor, the blow down vessel, and all other systems connected to the reactor. As a consequence, the reactor system becomes contaminated with oxygen.
  • the present disclosure provides a process for polymerizing ethylene, and optionally one or more comonomers, to obtain an ethylene-based polymer in a high-pressure polymerization system comprising
  • a reactor blow down system comprising a fluid communication system, adapted and ar ranged to be in fluid communication with the polymerization reactor via the fluid communi cation system, comprising
  • At least one first emergency valve arranged in the fluid communication system and adapted to open and close the fluid communication between the polymerization reac tor and the reactor blow down system
  • reactor blow down vessel is installed above the reactor blow down dump vessel, and wherein the process comprises
  • the reactor blow down system further comprises a blow down separator or a combination of blow down separator elements arranged and adapted for receiving the aqueous polymer slurry from the reactor blow down dump vessel and for separating the aque ous quenching medium from the polymer of the aqueous polymer slurry, and a circulation pump arranged and adapted to return the separated aqueous quenching medium to the blow down dump vessel, wherein the process further comprises the transfer of the aqueous polymer slurry from the reactor blow down dump vessel to the blow down separator or to the first element of the combination of blow down separator elements and the return of the separated aqueous quenching medium to the blow down dump vessel by use of the circulation pump.
  • the reactor blow down system b) further comprises
  • the high-pressure polymerization system further comprises c) a pressure control valve
  • a separation vessel or a cascade of separation vessels wherein the post reactor cooler is in fluid communication with the continuously operated polymeri zation reactor via a first connecting line, wherein the separation vessel or the cascade of separa tion vessels is in fluid communication with the post reactor cooler via a second connecting line, and wherein the pressure control valve is adapted and arranged to control the fluid communica tion between the continuously operated polymerization reactor and the post reactor cooler.
  • the high-pressure polymerization system further comprises a third connecting line between the reactor blow down vessel and the first connecting line, which branches off the first connecting line downstream of the pressure control valve, and a second emergency valve adapted and arranged to open and close the third connecting line in order to enable or prevent fluid communication with the reactor blow down vessel, and/or a fourth connecting line between the reactor blow down vessel and the second connecting line and a third emergency valve adapted and arranged to open and close the fourth connecting line in order to enable or prevent fluid communication with the reactor blow down vessel, wherein the process further comprises after step A) and prior to step C) instead of step B)
  • the reactor blow down vessel b1 further comprises at least one gas outlet.
  • the polymerization is restarted after the reactor blow down vessel has been emptied by transferring the aqueous poly mer slurry to the reactor blow down dump vessel and the first emergency valve or any combina tion of previously open emergency valves and the drain valve b4) have been closed.
  • the first emergency valve or any combination of previously open emergency valves are closed after step B) or B’) as long as the fluid communication system, or the fluid communication system and the third connecting line and/or fourth connecting line are ex periencing a positive pressure.
  • the reactor blow down vessel and the reactor blow down dump vessel are inside a protective enclosure and/or wherein the blow down separator or the combina tion of blow down separator elements and/or the circulation pump or the circulation pumps are outside a protective enclosure.
  • the at least one drain valve b4) is opened to transfer the aque ous polymer slurry to the reactor blow down dump vessel after the first emergency valve or any combination of previously open emergency valves have been closed.
  • the present disclosure further provides a high-pressure polymerization system com prising
  • a reactor blow down system adapted and arranged to be in fluid communication with the polymerization reactor via a fluid communication system comprising
  • a reactor blow down vessel b1
  • at least one first emergency valve arranged in the fluid communication system and adapted to open and close the fluid communication between the polymerization reac tor and the reactor blow down system
  • reactor blow down vessel is installed above, and being in fluid communication with the reactor blow down dump vessel.
  • the reactor blow down system further comprises a blow down separator or a combination of blow down separator elements arranged and adapted for receiving the aqueous polymer slurry from the reactor blow down dump vessel and for separating the aque ous quenching medium from the polymer of the aqueous polymer slurry, and a circulation pump arranged and adapted to return the separated aqueous quenching medium to the blow down dump vessel.
  • the reactor blow down system b) further comprises
  • the high-pressure polymerization system further comprises c) a pressure control valve,
  • a separation vessel or a cascade of separation vessels wherein the post reactor cooler is in fluid communication with the continuously operated polymeri zation reactor via a first connecting line, wherein the separation vessel or the cascade of separa tion vessels is in fluid communication with the post reactor cooler via a second connecting line, and wherein the pressure control valve is adapted and arranged to control the fluid communica tion between the continuously operated polymerization reactor and the post reactor cooler.
  • the high-pressure polymerization further comprises a third con necting line between the reactor blow down vessel and the first connecting line which branches off the first connecting line downstream of the pressure control valve and a second emergency valve adapted and arranged to open and close the third connecting line in order to enable or prevent fluid communication with the reactor blow down dump vessel, and/or a fourth connecting line between the reactor blow down vessel and the second connecting line and a third emergency valve adapted and arranged to open and close the fourth connecting line in order to enable or prevent fluid communication with the reactor blow down dump vessel.
  • Figure 1 shows schematically a set-up for carrying out the process of the present disclosure
  • Figure 2 depicts a schematic representation of an of the reactor blow down system of a con tinuously operable polymerization reactor.
  • the process of the present disclosure relates to a process for polymerizing ethylene, and optionally one or more comonomers, to obtain an ethylene-based polymer in a high-pressure polymerization system allowing to significantly reduce the duration of reactor shutdowns.
  • the effective operation time of a plant for the polymerization or copolymerization of ethyleni- cally unsaturated monomers can be significantly increased.
  • “and/or” is defined inclusively, such that the term “a and/or b” should be read to include the sets:“a and b”,“a or b”,“a”,“b”.
  • “and” in most cases“a and/or b” relates to two entities radiata“ and filingb”, wherein at least one of said entities is present in the embodiment described.
  • the present disclosure relates to a process for polymerizing ethylene, and optionally one or more comonomers, to obtain an ethylene-based polymer in a high-pressure polymerization system comprising a continuously operated polymerization reactor having an reactor inlet and having an reactor outlet, which can also be a combination of polymerization reactors.
  • the monomers are brought to the polymerization pressure by one or more compressors in a sequence of compression stages, the compressed monomers are optionally passed through a pre-heater or a pre-cooler and are then transferred into the polymerization reactor at the reactor inlet.
  • a reaction mixture obtained by the polymerization leaves the reactor at the reactor outlet through a pressure control valve and is op tionally cooled by an post reactor cooler. Subsequently, the reaction mixture is separated into polymeric and gaseous components in two or more stages, where the gaseous components sepa rated off in a first stage at an absolute pressure of from 15 MPa to 50 MPa are recycled to the one or more compressors via a high-pressure gas recycle line and the gaseous components sepa rated off in a second stage at an absolute pressure in the range of from 0.1 MPa to 0.5 MPa are recycled to the first stage of the sequence of compression stages via a low-pressure gas recycle line, and the polymeric components obtained by the polymerization are transformed into pellets.
  • the polymerization is preferably a homopolymerization of ethylene or a copolymeriza tion of ethylene with one or more other monomers, provided that these monomers are free-radi- cally copolymerizable with ethylene under high pressure.
  • copolymerizable mono mers for use in the present technology are a,b-unsaturated C3-Cs-carboxylic acids, derivatives of a,b-unsaturated C3-Cs-carboxylic acids, e.g. unsaturated C3-Cis-carboxylic esters or anhydrides, and 1 -olefins.
  • vinyl carboxylates such as vinyl acetate, can be used as comonomers.
  • Propene, 1 -butene, 1 -hexene, acrylic acid, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acry late, vinyl acetate or vinyl propionate are particularly suitable as comonomer.
  • the proportion of comonomer or comonomers in the reaction mixture is from 1 to 50% by weight, preferably from 3 to 40% by weight, based on the amount of monomers, i.e. the sum of ethylene and other monomers.
  • the comonomers are fed to the suction side of the secondary compressor.
  • polymers or polymeric materials are sub stances which are made up of at least two monomer units.
  • the polymers or polymeric materials are preferably low density polyethylenes having an average molecular weight M n of more than 20 000 g/mole.
  • the term "low density polyethylene” (LDPE) includes ethylene homopolymers and ethylene copolymers.
  • LDPE low density polyethylene
  • the process of the present disclosure can also be employed in the preparation of oligomers, waxes and polymers having a molecular weight Mn of less than 20 000 g/mole.
  • the process of the present disclosure is preferably a radical polymerization carried out in the presence of free-radical polymerization initiators.
  • Possible initiators for starting the polymerization in the respective reaction zones are in general any substances that can produce radical species under the conditions in the polymerization reactor, for example, oxygen, air, azo compounds or peroxidic polymerization initiators.
  • the polymerization is carried out by using oxygen, either fed in the form of pure O2 or as air.
  • the initiator is normally first mixed with the eth ylene feed and then fed to the reactor.
  • the molecular weight of the polymers to be prepared can as usual be altered by the addition of modifiers which act as chain-transfer agents.
  • modifiers for use in the present technology are hydrogen, aliphatic and olefinic hydrocarbons, e.g.
  • ketones such as acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone, methyl isoamyl ketone, di ethyl ketone or diamyl ketone, aldehydes such as formaldehyde, acetaldehyde or propionalde- hyde and saturated aliphatic alcohols such as methanol, ethanol, propanol, isopropanol or buta nol.
  • saturated aliphatic aldehydes in particular propio- naldehyde or 1 -olefins such as propene, 1 -butene or 1 -hexene, or aliphatic hydrocarbons such as propane.
  • the high polymerization is preferably carried out at pressures of from 1 10 MPa to 500 MPa, with pressures of from 160 MPa to 350 MPa being more preferred and pressures of from 200 MPa to 330 MPa being particularly preferred for polymerization in a tubular reactor and with pressures of from 1 10 MPa to 300 MPa being more preferred and pressures of from
  • the polymerization temperatures are preferably in the range of from 100°C to 350°C, and more preferably in the range of from 180°C to 340°C and particularly preferred from 200°C to 330°C for polymerization in a tubular reactor and more preferably in the range of from 1 10°C to 320°C and particularly preferred from 120°C to 310°C for polymerization in an autoclave reactor.
  • the polymerization can be carried out with all types of high-pressure reactors appropri ate for high-pressure polymerization.
  • High-pressure reactors for use in the present technology are, for example, tubular reactors or autoclave reactors.
  • the polymerization is carried out in one or more tubular reactors or one or more autoclave reactors or combinations of such re actors.
  • the polymerization reactor is a tubular reactor.
  • Common high-pressure autoclave reactors are stirred reactors and have a length-to- diameter ratio in a range from 2 to 30, preferably from 2 to 20.
  • Such autoclave reactors have one or more reaction zones, preferably from 1 to 6 reaction zones and more preferably from 1 to 4 re action zones. The number of reaction zones depends on the number of agitator baffles which separate individual mixed zones within the autoclave reactor.
  • high-pressure polymerization systems in which the polymerization or the first polymerization is carried out in an autoclave reac tor, i.e.
  • the reaction mixture coming from the compressors is usually first passed through a pre-cooler before entering the autoclave reactor.
  • Appropriate tubular reactors are basically long, thick-walled pipes, which are usually from about 0.5 km to 4 km, preferably from 1 km to 3 km and especially from 1 .5 km to 2.5 km long.
  • the inner diameter of the pipes is usually in the range of from about 30 mm to 120 mm and preferably from 60 mm to 100 mm.
  • Such tubular reactors have preferably a length-to-diameter ratio of greater than 1000:1 , preferably from 10000:1 to 40000:1 and especially from 25000:1 to 35000:1 .
  • Preferred tubular reactors have at least two reaction zones, preferably from 2 to 6 reac tion zones and more preferably from 2 to 5 reaction zones.
  • the number of reaction zones is giv en by the number of feeding points for the initiator.
  • a feeding point can, for example, be an injection point for a solution of azo compounds or organic peroxides.
  • Fresh initiator is added to the reactor, where the initiator decomposes into free radicals and initiates further polymerization. The generated heat of the reaction raises the temperature of the reaction mixture, since more heat is generated than can be removed through the walls of the tubular reactor.
  • the rising tem perature increases the rate of decomposition of the free-radical initiators and accelerates polymer ization until essentially all of the free-radical initiator is consumed. Thereafter, no further heat is generated and the temperature decreases again since the temperature of the reactor walls is lower than that of the reaction mixture. Accordingly, the part of the tubular reactor downstream of an initiator feeding point in which the temperature rises is the reaction zone, while the part there after, in which the temperature decreases again, is predominantly a cooling zone.
  • the amount and nature of added free-radical initiators determines how much the temperature rises and ac cordingly allows for adjusting that value.
  • the temperature rise is set to be in the range of from 70°C to 170°C in the first reaction zone and 50°C to 130°C for the subsequent reaction zones depending on the product specifications and the reactor configuration.
  • the tub ular reactor is equipped with cooling jackets for removing the heat of the reaction. More prefera bly, all reaction zones of the tubular reactor are cooled by cooling jackets.
  • the compression of the reaction gas composition to the polymerization pressure is car ried out by one or more compressors in a sequence of compression stages, where preferably a primary compressor first compresses the reaction gas composition to a pressure of from 10 MPa to 50 MPa and a secondary compressor further compresses the reaction gas composition to the polymerization pressure of from 1 10 MPa to 500 MPa.
  • the primary compressor and the secondary compressor are multistage compressors. It is further possible to separate one or more stages of one or both of these compressors and divide the stages into separated compres sors.
  • usually a series of one primary compressor and one secondary compressor is used for compressing the reaction gas composition to the polymerization pressure. In such cases, sometimes the whole primary compressor is designated as primary compressor.
  • the booster compressor which compress the recycle gas from the low- pressure product separator to the pressure of the fresh ethylene feed
  • the booster compressor and then only the one or more subsequent stages as the primary compressor, although the booster compressor and the subsequent stages are all part of one apparatus.
  • the high-pressure polymerization system comprises a pre-heater upstream of a tubular reactor for heating the reaction gas compo sition to a temperature capable of initiating the polymerization.
  • the entire reaction gas composition provided by the secondary compressor is fed via a pre-heater to the inlet of the tubular reactor.
  • only a part of the reaction gas composition compressed by the secondary com pressor is fed via the pre-heater to the inlet of the tubular reactor and the remainder of the reac tion gas composition compressed by the secondary compressor is fed as one or more side streams to the tubular reactor downstream of the inlet of the tubular reactor.
  • the high-pressure polymerization system for carrying out the polymerization of the pre sent disclosure preferably comprises, besides the polymerization reactor and the rector blow down system, two or more gas recycle lines for recycling unreacted monomers into the polymeri zation process.
  • the reaction mixture obtained in the polymerization reactor is transferred to a first separation vessel, frequently called high-pressure product separator, and separated into a gase ous fraction and a liquid fraction at an absolute pressure of from 15 MPa to 50 MPa.
  • the gase ous fraction withdrawn from the first separation vessel is fed via a high-pressure gas recycle line to the suction side of the secondary compressor.
  • the gas is usually purified by several purification steps for removing undesired components such as en trained polymer or oligomers.
  • the liquid fraction withdrawn from the first separation vessel which usually still comprises dissolved monomers such as ethylene and comonomers in an amount of 20 to 40% of weight, is transferred to a second separation vessel, frequently called low-pressure product separator, and further separated, at reduced pressure, usually at an absolute pressure in the range of from 0.1 MPa to 0.5 MPa, in polymeric and gaseous components.
  • the gaseous frac tion withdrawn from the second separation vessel is fed via a so-called low-pressure gas recycle line to the primary compressor, preferably to the foremost of the stages.
  • the low-pressure gas recycle line usually comprises several purification steps for purifying the gas from undesired components.
  • the high-pressure polymerization system can further comprise additional separa tion steps for separating additional gaseous fractions from the reaction mixtures and additional gas recycle lines for feeding such additional gaseous fractions comprising not reacted monomers to one of the compressors, for example in-between the first separation step and the second sepa ration step operating at an intermediate pressure.
  • the recycled gas coming from the low-pressure gas recycle line is com pressed by the first stages of the primary compressor to the pressure of the fresh feed of ethyleni- cally unsaturated monomers, preferably ethylene, and thereafter combined with the fresh gas feed and the combined gases are further compressed in the primary compressor to the pressure of from 10 MPa to 50 MPa.
  • the primary compressor comprises five or six compression stages, two or three before adding the fresh gas and two or three after adding the fresh gas.
  • the secondary compressor has preferably two stages; a first stage, which compresses the gas to a pressure in the range from 50 MPa to 150 MPa, and a second stage, which further compresses the gas to the final polymerization pressure.
  • the pressure within the polymerization reactor is preferably controlled by a pressure control valve, which is arranged at the outlet of the polymerization reactor and through which the reaction mixture leaves the reactor.
  • the pressure control valve can be any valve arrangement which is suitable for reducing the pressure of the reaction mixture leaving the reactor to the pres sure within the first separation vessel.
  • the high-pressure polymerization system comprises a post reactor cooler downstream of the polymerization reactor for cooling the reaction mixture.
  • the post reactor cooler can be arranged upstream of the pressure control valve or the post reactor cooler can be arranged downstream of the pressure control valve.
  • the post reactor cooler is arranged downstream of the pressure control valve.
  • Preferred polymerization reactors are located in a chamber having a surrounding pro tective wall.
  • the polymeric components obtained by the polymerization are finally transformed into pellets, normally by apparatuses like extruders or granulators.
  • the ethylene-based polymer produced by the process is a LDPE having a density in the range from 0.910 g/cm 3 to 0.940 g/cm 3 .
  • the process of the present disclosure is characterized in that the high-pressure polymerization system comprises, besides
  • a reactor blow down system comprising a fluid communication system, adapted and ar ranged to be in fluid communication with the polymerization reactor via the fluid communi cation system, comprising
  • At least one first emergency valve preferably a multitude of first emergency valves distributed over the length of the operated high-pressure tubular reactor, and ar ranged in the fluid communication system and adapted to open and close the fluid communication between the polymerization reactor and the reactor blow down sys tem,
  • reactor blow down vessel is installed above the reactor blow down dump vessel, and wherein the process comprises
  • the high-pressure polymerization system is monitored with respect to an occurrence of a disturbance.
  • the least one first emergency valve is opened and the content of the polymerization system compris ing polymer and gaseous components is expand into the reactor blow down vessel.
  • the high-pressure polymerization is interrupted in a controlled manner.
  • a disturbance in the context of the present disclosure is any deviation of the normal polymerization conditions which is deemed significant enough that the polymerization has to be terminated.
  • the monitoring of the high-pressure polymerization system occurs by measuring various parameters with respect to the conditions of the high-pressure polymerization system. These parameters include pres sures and temperatures at various positions of the polymerization system, filling levels of vessels, positions of valves, hydrocarbon concentrations in the surrounding of the high-pressure polymeri zation system and vibrations in the polymerization system. If one of these parameter deviates sig nificantly from the normal values, for example by differing more than 10% from a usually meas ured value, an occurrence of a disturbance is established and step B) of the process is carried out.
  • the at least one drain valve b4) is remotely operated or operable.
  • the at least one drain valve b4) is opened to transfer the aqueous polymer slurry to the reactor blow down dump vessel after the first emergency valve or any combination of previously open emergency valves have been closed.
  • the reactor blow down system used in the process of the present disclosure further comprises a blow down separator or a combination of blow down separator elements ar ranged and adapted for receiving the aqueous polymer slurry from the reactor blow down dump vessel and for separating the aqueous quenching medium from the polymer of the aqueous poly mer slurry, and a circulation pump arranged and adapted to return the separated aqueous quenching medium to the blow down dump vessel, wherein the process further comprises the transfer of the aqueous polymer slurry from the reactor blow down dump vessel to the blow down separator or to the first element of the combination of blow down separator elements and the re turn of the separated aqueous quenching medium to the blow down dump vessel by use of the circulation pump.
  • a blow down separator or a combination of blow down separator elements ar ranged and adapted for receiving the aqueous polymer slurry from the reactor blow down dump vessel and for separating the aqueous quenching medium from the polymer of the a
  • the transfer of the aqueous polymer slurry from the reactor blow down dump vessel to the blow down separator or to the first element of the combination of blow down separa tor elements may occur by gravity or by a pump which may be the circulation pump, which also returns the separated aqueous quenching medium to the blow down dump vessel; or the pump, which transfer the aqueous polymer slurry from the reactor blow down dump vessel to the blow down separator or to the first element of the combination of blow down separator elements, is a different pump than the pump, which returns the separated aqueous quenching medium to the blow down dump vessel.
  • the separation of the aqueous polymer slurry into an aqueous phase and wet polymer occurs by a combination of blow down separator elements.
  • the combination of blow down separator elements is a combination of two blow down separator elements, where the first element is a buffer vessel for holding the aqueous polymer slurry in a suitable spatial arrangement to the second element com bination of blow down separator elements and the second element is a separating devices such as a centrifuge or a sieving devise like an inclined sieve.
  • the reactor blow down vessel b1 further comprises at least one gas outlet for removing the gaseous components having been separated from the aqueous polymer slurry.
  • the reactor blow down vessel is nitrogen blanketed although being open to the atmos phere.
  • the reactor blow down system b) used in the process of the present disclosure further comprises
  • a nitrogen blanketing system preferably nitrogen blanketing the reactor blow down vessel and nitrogen blanketing the reactor blow down dump vessel
  • a pressure control system preferably controlling the pressure of the reactor blow down dump vessel, and/or
  • a til-level control system preferably controlling the filling level of the reactor blow down ves sel and controlling the filling level of the reactor blow down dump vessel.
  • the high-pressure polymeri zation system used in the process of the present disclosure further comprises
  • a separation vessel or a cascade of separation vessels preferably a first separation vessel and a second separation vessel in series
  • the post reactor cooler is in fluid communication with the continuously operated polymeriza tion reactor via a first connecting line, wherein the separation vessel or the cascade of separation vessels is preferably also in fluid communication with the post reactor cooler via a second con necting line, and wherein the pressure control valve is adapted and arranged to control the fluid communication between the continuously operated polymerization reactor and the post reactor cooler.
  • the high-pressure polymerization system preferably further com prises a third connecting line between the reactor blow down vessel and the first connecting line, which branches off the first connecting line downstream of the pressure control valve, and a sec ond emergency valve adapted and arranged to open and close the third connecting line in order to enable or prevent fluid communication with the reactor blow down vessel , and/or a fourth con necting line between the reactor blow down vessel and the second connecting line and a third emergency valve adapted and arranged to open and close the fourth connecting line in order to enable or prevent fluid communication with the reactor blow down vessel, wherein the process further comprises after step A) and prior to step C) instead of step B)
  • the polymerization is restarted after the reactor blow down vessel has been emptied by transferring the aqueous polymer slurry to the reactor blow down dump vessel and the first emer gency valve or any combination of previously open emergency valves and the drain valve b4) have been closed.
  • the first emergency valve or any combination of previously open emergency valves are closed after step B) or B’) as long as the fluid communication system, or the fluid communication system and the third connecting line and/or fourth connecting line are experiencing a positive pressure.
  • the reactor blow down vessel and the reactor blow down dump vessel are inside a protective enclosure, frequently called“reactor bay”, and/or wherein the blow down separator or the combination of blow down separator ele ments and/or the circulation pump or the circulation pumps are outside a protective enclosure.
  • the at least one drain valve b4) is opened, preferably remotely opened, to transfer the aqueous polymer slurry to the reactor blow down dump vessel after the first emergency valve or any combination of previously open emer gency valves have been closed.
  • the aqueous quenching medium in most cases is water.
  • the aqueous quenching medium in addition to water also comprises at least one polymerization inhibitor such as hydroquinone or pH buffer agents.
  • Suitable buffer agents comprise for example phosphate buffers, e.g. obtained by mixing sodium hydrogen phosphate and sodium hydroxide.
  • the process of the present disclosure also relates to a high-pressure polymerization system comprising
  • a reactor blow down system adapted and arranged to be in fluid communication with the polymerization reactor via a fluid communication system comprising
  • At least one first emergency valve arranged in the fluid communication system and adapted to open and close the fluid communication between the polymerization reactor and the re actor blow down system
  • a reactor blow down dump vessel arranged and adapted to be in fluid communication with the reactor blow down vessel, b4) at least one drain valve in the fluid communication between the reactor blow down vessel and the reactor blow down dump vessel adapted and arranged to close the reactor blow down vessel in order to enable or prevent fluid communication with the reactor blow down dump vessel,
  • the reactor blow down vessel is installed above, and being in fluid communication with the reactor blow down dump vessel.
  • the reactor blow down system further comprises a blow down separator or a combination of blow down separator elements arranged and adapted for receiving the aqueous polymer slurry from the reactor blow down dump vessel and for separat ing the aqueous quenching medium from the polymer of the aqueous polymer slurry, and a circu lation pump arranged and adapted to return the separated aqueous quenching medium to the blow down dump vessel.
  • the reactor blow down system b) of the high-pressure polymerization system further comprises
  • a nitrogen blanketing system preferably nitrogen blanketing the reactor blow down vessel and nitrogen blanketing the reactor blow down dump vessel
  • a pressure control system preferably controlling the pressure of the reactor blow down dump vessel, and/or
  • a fil-level control system preferably controlling the filling level of the reactor blow down ves sel and controlling the filling level of the reactor blow down dump vessel.
  • the high-pressure polymeri zation system further comprises
  • a separation vessel or a cascade of separation vessels preferably a first separation vessel and a second separation vessel in series
  • the post reactor cooler is in fluid communication with the continuously operated polymeriza tion reactor via a first connecting line, wherein the separation vessel or the cascade of separation vessels is preferably also in fluid communication with the post reactor cooler via a second con necting line, and wherein the pressure control valve is adapted and arranged to control the fluid communication between the continuously operated polymerization reactor and the post reactor cooler.
  • the high-pressure polymerization system preferably further com prises a third connecting line between the reactor blow down vessel and the first connecting line, which branches off the first connecting line downstream of the pressure control valve, and a sec ond emergency valve adapted and arranged to open and close the third connecting line in order to enable or prevent fluid communication with the reactor blow down dump vessel , and/or a fourth connecting line between the reactor blow down vessel and the second connecting line and a third emergency valve adapted and arranged to open and close the fourth connecting line in order to enable or prevent fluid communication with the reactor blow down dump vessel.
  • Figure 1 shows schematically a set-up of a high-pressure polymerization system for polymerizing ethylenically unsaturated monomers in a high-pressure polymerization system com prising a continuously operated tubular polymerization reactor (6) and the reactor blow down sys tem (29) of the process and the high-pressure polymerization system of the present disclosure.
  • the fresh ethylene which depending on the supply conditions may be under a pressure of for example 1 .7 MPa or 12 MPa, is firstly compressed to a significantly higher pressure, e.g. of about 30 MPa by means of a primary compressor (1 ) and then compressed to the reaction pres sure of about 300 MPa using a secondary compressor (2).
  • Chain transfer agents (CTA) may in one embodiment be added to primary compressor (1 ) together with the fresh ethylene.
  • Comono mer may be added upstream of the secondary compressor (2) via line (3).
  • the reaction mixture leaving the primary compressor (2) is fed to pre-heater (4), where the reaction mixture is pre heated to the reaction start temperature, e.g. of from about 120°C to 220°C, and then conveyed to the inlet (5) of the tubular reactor (6).
  • the tubular reactor (6) is basically a long, thick-walled pipe with cooling jackets to re move the liberated heat of reaction from the reaction mixture by means of a coolant circuit (not shown).
  • the exemplary embodiment of a tubular reactor (6) as shown in Figure 1 has four spa tially separated initiator injection points (7a), (7b), (7c), and (7d) for feeding initiators or initiator mixtures PX1 , PX2, PX3 and PX4 to the reactor and accordingly also four reaction zones.
  • initiators or initiator mixtures PX1 , PX2, PX3 and PX4 to the reactor and accordingly also four reaction zones.
  • the reaction mixture leaves the tubular reactor (6) through pressure control valve (8) being incorporated in the first connecting line (50) and passes a post reactor cooler (9). Thereaf ter, the cooled reaction mixture is transferred via a second connecting line (54) to a first separa tion vessel (10).
  • a first separa tion vessel (10) By use of this first separation vessel (10) and of a second separation vessel (1 1 ), the resulting polymer is separated off from unreacted ethylene and other low molecular weight compounds (monomers, oligomers, polymers, additives, solvent, etc.), discharged and pelletized via an extruder and granulator (12).
  • the ethylene and comonomers which have been separated off in the first separation vessel (1 0) are fed back to the inlet end of the tube reactor (6) in the high-pressure circuit (13), e.g. at about 30 MPa.
  • the high-pressure circuit (13) the gaseous material separated from the reaction mixture is first freed from other constituents in at least one purification stage and then added to the monomer stream between primary compressor (1 ) and secondary compressor (2).
  • Figure 1 shows one purification stage consisting of a heat exchanger (14) and a separator (15). It is however also possible to use a plurality of purification stages, e.g. arranged in parallel.
  • the high-pressure circuit (13) usually separates waxes.
  • Figure 1 shows two purification stages consisting of heat exchangers (17) and (19) and separators (18) and (20). It is however also possible to use only one purification stages or preferably more than two purification stages.
  • the low-pressure cir cuit (16) usually separates oils and waxes.
  • Booster compressor (21 ) and primary compressor (1 ) are preferably part of one low- pressure compressor, i.e. of one apparatus powered by one motor.
  • the high-pressure polymerization system also comprises a reactor blow down system (29) comprising a reactor blow down vessel (31 ).
  • the reactor blow down system (29) can be brought in fluid communication which the polymerization reactor (6) by use of one or more con necting lines (46) having a first emergency valves (32i), a third connecting line (42) having a sec ond disturbance valve (32j) and/or a fourth connecting line (44) having a third disturbance valve (32k).
  • the reactor blow down vessel (31 ) is installed above a reactor blow down dump vessel (33).
  • FIG. 2 Details of an embodiment of the reactor blow down system (29) are shown in Figure 2.
  • the embodiment depicted in Figure 2 has a reactor blow down vessel (31 ); a fluid communication system (40) comprising a first emergency valve (32i) incorporated into a connecting line (46), a second emergency valve (32j) incorporated into a third connecting line (42), a third emergency valve (32k) incorporated into a fourth connecting line (44); and a reactor blow down dump vessel (33).
  • the first emergency valve (32i) can also be considered to be a placeholder for a multitude of first emergency valves(32i), each being incorporated into a separate connecting line (46) and each being part of the fluid communication system (40).
  • the connecting line (46), the third connecting line (42) and the fourth connecting line (44) all lead into the upper half of the side wall of the reactor blow down vessel (31 ).
  • the reactor blow down vessel (31 ) is located on top of the reactor blow down dump vessel (33) and is in fluid communication therewith.
  • the first emergency valve (32i) is opened and the content of the polymeriza tion reactor (6) is expanded into the reactor blow down vessel (31 ) containing an aqueous quenching medium.
  • the second emergency valve (32j) and the third emergency valve (32k) are opened and the content of the connecting line (46) start ing from the outlet (30) of the polymerization reactor (6) and that of the post reactor cooler (9) are also expanded into the reactor blow down vessel (31 ).
  • the first emergency valve (32i), the second emergency valve (32j) and the third disturbance (32k) valve are simultaneously opened in case of a disturbance.
  • the polymer obtained in the polymerization reactor is solidified, usually in the form of flakes. Concomitantly, the temperature of both of the polymeric and the gaseous components is reduced.
  • the reactor blow down vessel (31 ) the wa ter/polymer mixture and the gaseous components can be separated by releasing the gaseous components via a respective outlet or vent (48). After release of the gaseous components, the remaining water/polymer mixture is transferred into the reactor blow down dump vessel (33) by gravity upon opening of the drain valve (34).
  • the drain valve (34) is closed.
  • the successful transfer of the polymer/water slurry can be surveyed by a camera system (not shown), mounted on the reactor blow down vessel (31 ).
  • the reactor blow down system (29) further comprises a combination of blow down separator elements (35) and (37) and a circulation pump (36) by use of which the aqueous quenching medium separated from the water/polymer slurry is returned to the reactor blow down dump vessel (33).
  • the first element (35) of the combi nation of blow down separator elements is a buffer vessel to which the content of reactor blow down dump vessel (33) can be transferred by gravity, in some cases supported by nitrogen.
  • the second element (37) of the combination of blow down separator elements is an inclined sieve which is used for retaining the polymer. Also the transfer of the water/polymer slurry from buffer vessel (35) to sieve (37) occurs by gravity.
  • the aqueous phase separated from the water/polymer slurry by sieve (37) is then conveyed via line (38) by use of circulation pump (36) to the reactor blow down dump vessel (33).
  • This circulation of water is kept in operation until all polymer waste from the reactor blow down dump vessel (33) is removed and was finally retained by inclined sieve (37).
  • the steps of depressurizing the polymerization reactor and purging the blow down vessel and the polymerization reactor both prior and after emptying the blow down vessel become unnecessary and manual operator intervention is not needed.
  • the content of the polymerization system is expanded into the reactor blow down vessel and contacted with the aqueous quenching system.
  • the pressure in the continuous high-pressure polymerization system can be rapidly reduced, e.g. within a minute or even less from about or above 200 MPa to 0.1 MPa.
  • the gaseous com ponents are released from this vessel, the water/polymer mixture is, in some cases automatically, transferred into the reactor blow down dump vessel.
  • the polymerization can restart immediately after the reactor blow down vessel has been emptied, i.e. after a much shorter time period than according to established pressure reducing processes.
  • the reactor can be automatically depressurized by automatically opening the least one emergency valve in case of any disturbance or emergency thereby putting the reactor into safe condition. That is, polymerization can not only be stopped safely in case of an emergency like fire, explosion, earthquake or polyethylene decomposition but also if devia tions, i.e. disturbances, from the standard operating conditions, e.g. by exceeding pre-defined threshold values, are detected.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de polymérisation d'éthylène dans un système de polymérisation haute pression comprenant un réacteur de polymérisation fonctionnant en continu et un système de purge de réacteur comprenant une vanne d'urgence, une cuve de purge de réacteur contenant un milieu aqueux et une cuve de purge de réacteur, le procédé consistant à surveiller le système de polymérisation quant à l'apparition d'une perturbation, à ouvrir la vanne d'urgence en cas de perturbation afin de permettre au contenu du système de polymérisation de se dilater dans la cuve de purge de réacteur, à mettre en contact un contenu dans la cuve de purge de réacteur avec le milieu aqueux afin d'obtenir une suspension aqueuse de polymère, à séparer la suspension de polymère et des constituants gazeux et à transférer la suspension de polymère vers la cuve de purge de réacteur.
PCT/EP2019/085394 2018-12-18 2019-12-16 Procédé de polymérisation haute pression de monomères à insaturation éthylique dans un réacteur de polymérisation WO2020127079A1 (fr)

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CN201980078729.1A CN113166283B (zh) 2018-12-18 2019-12-16 烯键不饱和单体在聚合反应器中的高压聚合方法
EP19818105.9A EP3898708B1 (fr) 2018-12-18 2019-12-16 Procédé de polymérisation haute pression de monomères éthyléniquement insaturés dans un réacteur de polymérisation
US17/312,288 US20220106418A1 (en) 2018-12-18 2019-12-16 High-pressure polymerization process of ethylenically unsaturated monomers in a polymerization reactor

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EP0266543A2 (fr) 1986-10-04 1988-05-11 BASF Aktiengesellschaft Système de séparation pour réduire l'émission de solides lors des procédés de relaxation dans des réacteurs de polymérisation à haute pression
EP0272512A2 (fr) 1986-12-04 1988-06-29 BASF Aktiengesellschaft Procédé pour réduire l'émission d'hydrocarbures lors des procédés de relaxation dans les réacteurs de polymérisation à haute pression
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EP3898708B1 (fr) 2022-06-15
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EP3898708A1 (fr) 2021-10-27

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